Laminate

ABSTRACT

The present application relates to a block copolymer and a use thereof. The present application can provide a laminate which is capable of forming a highly aligned block copolymer on a substrate and thus can be effectively applied to production of various patterned substrates, and a method for producing a patterned substrate using the same.

TECHNICAL FIELD

This application claims the benefit of priority based on Korean PatentApplication No. 10-2016-0162140 filed on Nov. 30, 2016, the disclosureof which is incorporated herein by reference in its entirety.

The present application relates to a laminate.

BACKGROUND ART

A block copolymer has a molecular structure in which polymer segmentshaving different chemical structures are linked via covalent bonds. Theblock copolymer can form a periodically arranged structure such as asphere, a cylinder or a lamella by phase separation. The domain size ofthe structure formed by a self-assembly phenomenon of the blockcopolymer can be widely controlled and various types of structures canbe manufactured, so that the block copolymer can be applied to highdensity magnetic storage media, nanowire fabrication, variousnext-generation nano devices such as quantum dots or metal dots ormagnetic recording media, or pattern formation by lithography, and thelike.

DISCLOSURE Technical Problem

The present application provides a laminate.

Technical Solution

In this specification, the term alkyl group may mean an alkyl grouphaving 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms,1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified.The alkyl group may be a linear, branched or cyclic alkyl group, whichmay be optionally substituted with one or more substituents.

In this specification, the term alkoxy group may mean an alkoxy grouphaving 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms,1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified.The alkoxy group may be a linear, branched or cyclic alkoxy group, whichmay be optionally substituted with one or more substituents.

The term alkenyl group or alkynyl group herein means an alkenyl group oralkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbon atoms, unlessotherwise specified. The alkenyl or alkynyl group may be linear,branched or cyclic, which may be optionally substituted with one or moresubstituents.

The term alkylene group herein may mean an alkylene group having 1 to 20carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbonatoms or 1 to 4 carbon atoms, unless otherwise specified. The alkylenegroup may be a linear, branched or cyclic alkylene group, which may beoptionally substituted with one or more substituents.

The term alkenylene group or alkynylene group herein may mean analkenylene group or alkynylene group having 2 to 20 carbon atoms, 2 to16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4carbon atoms. The alkenylene group or alkynylene group may be linear,branched or cyclic, which may be optionally substituted with one or moresubstituents.

The term aryl group or arylene group herein may mean, unless otherwisespecified, a monovalent residue or divalent residue derived from acompound comprising one benzene structure, or a structure in which twoor more benzene rings are linked while sharing one or two carbon atoms,or linked by any linker, or a derivative thereof. The aryl group orarylene group may be, for example, an aryl group having 6 to 30 carbonatoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atomsor 6 to 13 carbon atoms, unless otherwise specified.

In the present application, the term aromatic structure may mean thearyl group or arylene group.

In this specification, the term alicyclic ring structure means a cyclichydrocarbon structure other than an aromatic ring structure, unlessotherwise specified. The alicyclic ring structure may be, for example,an alicyclic ring structure having 3 to 30 carbon atoms, 3 to 25 carbonatoms, 3 to 21 carbon atoms, 3 to 18 carbon atoms or 3 to 13 carbonatoms, unless otherwise specified.

In the present application, the term single bond may mean a case whereno separate atom is present at the relevant site. For example, in thestructure represented by A-B-C, when B is a single bond, no separateatom exists at the site represented by B, and A and C are directlyconnected, so that it may mean to form a structure represented by A-C.

In the present application, the substituent, with which the alkyl group,alkenyl group, alkynyl group, alkylene group, alkenylene group,alkynylene group, alkoxy group, aryl group, arylene group, chain oraromatic structure, and the like may be optionally substituted, may beexemplified by a hydroxy group, a halogen atom, a carboxyl group, aglycidyl group, an acryloyl group, a methacryloyl group, an acryloyloxygroup, a methacryloyloxy group, a thiol group, an alkyl group, analkenyl group, an alkynyl group, an alkylene group, an alkenylene group,an alkynylene group, an alkoxy group or an aryl group, and the like, butis not limited thereto.

The present application relates to a laminate. The laminate of thepresent application may be applied to a method for producing a patternedsubstrate. The method for producing the patterned substrate of thepresent application may be performed by a lithography method in which adirected self-assembly material is applied as a template, where thedirected self-assembly material may be a block copolymer.

The laminate of the present application allows a self-assembledstructure of the directed self-assembly material to be formed withhigher precision in the process of producing the patterned substrate asabove, thereby precisely performing patterning of the substrate.

The laminate of the present application comprises: a substrate; apolymer stripe pattern formed on the substrate and a block copolymerfilm formed on the surface of the substrate on which the polymer stripepattern is formed.

In the laminate of the present application, no neutral treatment regionmay be included between the substrate and the block copolymer film. Inthe present application, the term neutral treatment region is atreatment region known as a so-called neutral brush layer or the like inthe industry, which includes all treatment regions known as beingcapable of achieving the vertical orientation of the block copolymer onthe substrate. That is, in the laminate of the present application, theblock copolymer film may be in direct contact with the substrate or thepolymer stripe pattern.

The type of the substrate included in the laminate of the presentapplication is not particularly limited. This substrate may be etchedvia a mask formed by a block copolymer film in a method formanufacturing a patterned substrate to be described below. As such asubstrate, for example, various types of substrates requiring formationof a pattern on the surface may all be used. This type of substrate mayinclude, for example, a silicon substrate, a silicon germaniumsubstrate, a GaAs substrate, a silicon oxide substrate, and the like. Asthe substrate, for example, a substrate applied to formation of finFETs(fin field effect transistors) or other electronic devices such asdiodes, transistors or capacitors may be used. In addition, othermaterials such as ceramics may be used as the substrate depending on theapplication, and the types of substrates that can be applied in thepresent application are not limited thereto.

In the present application, the polymer stripe pattern is formed on thesurface of the substrate as above. For example, as schematically shownin FIG. 1, the polymer stripe pattern means a form in which two or morestripe shaped polymer films (20) are formed on the surface of thesubstrate (10) to form a pattern.

The block copolymer film is formed on the surface of the substrate onwhich the polymer stripe pattern as above is formed. In the blockcopolymer film, the block copolymer forms a self-assembled structure.The type of the self-assembled structure formed by the block copolymeris not particularly limited, which may be a known self-assembledstructure, for example, a structure such as a sphere, a cylinder or alamella, and in one example, may be a lamellar structure.

The present inventors have confirmed that a highly preciseself-assembled structure can be formed on a substrate by controlling thepolymer stripe pattern and the type and shape of the block copolymer inthe structure of such a laminate, as described below.

For example, the shape of the polymer stripe pattern in the laminate canbe controlled as follows.

For example, when the self-assembled structure formed by the blockcopolymer in the block copolymer film of the laminate is a lamellarstructure, the polymer stripe pattern may have a stripe width of 0.3 Lto 2.0 L, 0.3 L to 1.8 L, 0.3 L to 1.6 L, 0.3 L to 1.4 L, 0.3 L to 1.2L, 0.3 L to 1.0 L, 0.3 L to 0.8 L, 0.3 L to 0.7 L, 0.4 L to 0.6 L orabout 0.5 L to 0.6 L, or about 0.5 L or so. Here, L is a pitch of thelamellar structure formed by the block copolymer. Also, here, the stripewidth is indicated by W in FIG. 1, for example.

Furthermore, the ratio (F/W) of the stripe pitch (F) to the stripe width(W) in the polymer stripe pattern may be in a range of 2 to 20. Here,the stripe pitch is a distance between the start point of any one stripeand the start point of another stripe adjacent thereto, which isindicated by F in FIG. 1. In another example, the ratio (F/W) may beabout 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more,9 or more, 10 or more, 11 or more, 12 or more or 13 or more, or 14 ormore, or may be about 19 or less, 18 or less, 17 or less, or 16 or less.

In the laminate, the polymer stripe pattern may have a thickness of 50nm or less. In another example, the thickness of the polymer stripepattern may be about 45 nm or less, about 40 nm or less, about 35 nm orless, about 30 nm or less, about 25 nm or less, about 20 nm or less,about 15 nm or less, or about 10 nm or less, and optionally, may beabout 0.5 nm or more, about 1 nm or more, about 2 nm or more, about 3 nmor more, about 4 nm or more, about 5 nm or more, about 6 nm or more,about 7 nm or more, about 8 nm or more, or about 9 nm or more.

In another example, the thickness of the polymer stripe pattern may be Lor less. In another example, the thickness of the polymer stripe patternmay be about 0.9 L or less, about 0.8 L or less, about 0.7 L or less, orabout 0.6 L or less, and optionally, may be about 0.01 L or more, 0.05 Lor more, 0.1 L or more, 0.2 L or more, 0.3 L or more, 0.4 L or more, orabout 0.5 L or more. In such a range, appropriate effects may beexhibited. Here, L is a pitch of the lamellar structure formed by theblock copolymer.

In the laminate, the thickness of the block copolymer film can beadjusted in the range of 1 L to 10 L. Here, L is a pitch of the lamellarstructure formed by the block copolymer. In another example, thethickness may be about 9 L or less, 8 L or less, 7 L or less, 6 L orless, 5 L or less, 4 L or less, 3 L or less or 2 L or less.

The polymer segment A contained in such a laminate and the polymersegment B different from the polymer segment A may be included.

In the present application, the fact that two kinds of polymer segmentsare identical means any one case of cases in which in any two kinds ofpolymer segments the kinds of monomer units contained as the maincomponent are identical to each other, or 50% or more, 55% or more, 60%or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or moreor 90% or more of monomer unit kinds contained in two kinds of polymersegments are common and a weight ratio deviation of the common monomerunits in each polymer segment is within 30%, within 25%, within 20%,within 20%, within 15%, within 10% or within 5%. Here, the monomer unitthat the polymer segment comprises as a main component is a monomer unitin which 60% or more, 65% or more, 70% or more, 75% or more, 80% ormore, 85% or more, or 90% or more is included and 100% or less isincluded in the corresponding polymer segment. If both polymer segmentsdo not satisfy the two cases, they are polymer segments that aredifferent from each other. Here, it may be proper that the ratio of thecommon monomer units is satisfied for both polymer segments. Forexample, if any polymer segment 1 has monomer units of A, B, C, D and Fand the other polymer segment 2 has monomer units of D, F, G and H, thenthe common monomer units in polymer segments 1 and 2 are D and F, wherein the position of polymer segment 1 the common ratio is 40% (=100×2/5)because two kinds of the total five kinds are common, but in theposition of polymer segment 2 the ratio is 50% (=100×2/5). Thus, in thiscase, both polymer segments may be regarded as not identical because thecommon ratio is not less than 50% only in polymer segment 2. On theother hand, the weight ratio deviation of the common monomers is apercentage of a numerical value in which a large weight ratio minus asmall weight ratio is divided by the small weight ratio. For example, inthe above case, if the weight ratio of the D monomer units in thesegment 1 is about 40% based on 100% of the total weight ratio of thewhole monomer units in the segment 1 and the weight ratio of the Dmonomer units in the segment 2 is about 30% based on 100% of the totalweight ratio of the whole monomer units in the segment 2, the weightratio deviation may be about 33% (=100×(40−30)/30) or so. If the commonmonomer units are two or more kinds in two segments, in order to be thesame segment, it can be considered as the common monomers when theweight ratio deviation within 30% is satisfied for all the commonmonomers or for the monomer unit as the main component. Each polymersegment that is recognized as the same by the above criteria may be adifferent type of polymer (e.g., any one segment is in the form of ablock copolymer and the other segment is in the form of a randomcopolymer), but it may be, suitably, the same type of polymer.

The respective polymer segments of the block copolymer may be formed byonly one monomer, or may be formed by two or more of monomers. The blockcopolymer may be a diblock copolymer comprising only one polymer segmentA and one polymer segment B. The block copolymer may also be a blockcopolymer of three blocks or more which comprises each one of thepolymer segments A and B, and further comprises any one or both of thepolymer segments A and B, or further comprises other polymer segmentsrather than the polymer segments A and B.

The block copolymer comprises two or more polymer segments connected bycovalent bonds, and thus phase separation occurs and a so-calledself-assembled structure is formed. The present inventors have confirmedthat the block copolymer can be more effectively applied in the laminateby satisfying any one or two or more of conditions to be describedbelow. Accordingly, the block copolymer of the present application maysatisfy at least one of the following conditions. The conditionsdescribed below are in parallel, and any one condition does not overridethe other conditions. The block copolymer may satisfy any one conditionselected from the conditions described below, or may satisfy two or moreconditions. Through the fulfillment of any one condition, the blockcopolymer can exhibit more effectively vertical orientation in theabove-described laminate. In the present application, the term verticalorientation indicates the orientation of the block copolymer, where theorientation of the phase separation structure or the self-assembledstructure formed by the block copolymer may mean an orientationperpendicular to the substrate direction, and for example, may mean acase where the interface between the domain formed by a polymer segmentA and the domain formed by a polymer segment B, which are describedbelow, of the block copolymer is perpendicular to the surface of thesubstrate. In the present application, the term vertical is anexpression in consideration of an error, which may be a meaningincluding, for example, errors within ±10 degrees, ±8 degrees, ±6degrees, ±4 degrees or ±2 degrees.

An exemplary block copolymer of the present application comprises apolymer segment A and a polymer segment B different from the polymersegment A, wherein the block copolymer or the polymer segment A mayexhibit a melting transition peak or an isotropic transition peak in arange of −80° C. to 200° C. in a DSC analysis (Condition 1).

An exemplary block copolymer of the present application comprises apolymer segment A and a polymer segment B different from the polymersegment A, wherein the block copolymer or the polymer segment A mayexhibit a peak having a half-value width in a range of 0.2 to 0.9 nm⁻¹within a scattering vector (q) range of 0.5 nm⁻¹ to 10 nm⁻¹ upon an XRDanalysis (Condition 2).

An exemplary block copolymer of the present application comprises apolymer segment A and a polymer segment B different from the polymersegment A, wherein the polymer segment A may comprise a side chain andthe number (n) of chain-forming atoms in the side chain and thescattering vector (q) obtained by the XRD analysis of the polymersegment A may satisfy Equation 1 below (Condition 3).

3 nm⁻¹ to 5 nm⁻¹ =nq/(2×π)  [Equation 1]

In Equation 1, n is a number of chain-forming atoms of the side chain,and q is the smallest scattering vector (q) in which the peak isobserved in the X-ray diffraction analysis for the polymer segmentcontaining the side chain, or the scattering vector (q) in which thepeak of the largest peak area is observed.

An exemplary block copolymer of the present application comprises apolymer segment A and a polymer segment B different from the polymersegment A, wherein the absolute value of the difference between thesurface energy of the polymer segment A and the surface energy of thepolymer segment B may be 10 mN/m or less (Condition 4).

An exemplary block copolymer of the present application comprises apolymer segment A and a polymer segment B different from the polymersegment A, wherein the absolute value of the difference in densitybetween the polymer segment A and the polymer segment B may be 0.25g/cm³ or more (Condition 5).

In the respective block copolymers, the polymer segment A may be apolymer segment comprising a side chain as described below.

Hereinafter, each of the conditions will be described in detail.

In this specification, physical properties, such as density, that can bechanged by temperature are values measured at room temperature, unlessotherwise specified. The term room temperature is a natural temperaturewithout warming or cooling, which may mean a temperature of about 10° C.to 30° C., about 25° C. or about 23° C.

Also, in this specification, unless otherwise specified, the unit oftemperature is ° C.

A. Condition 1

The block copolymer of the present application or any one polymersegment of the block copolymer may exhibit a melting transition peak orisotropic transition peak in a range of −80° C. to 200° C. in a DSC(differential scanning calorimetry) analysis. The block copolymer or anyone polymer segment of the block copolymer may also exhibit only any onepeak of the melting transition peak or the isotropic transition peak, ormay exhibit both of the two peaks. Such a block copolymer may be acopolymer exhibiting a crystal phase and/or a liquid crystal phasesuitable for self-assembly as a whole or comprising a polymer segmentexhibiting such a crystal phase and/or a liquid crystal phase. Thepolymer segment satisfying Condition 1 above may be a polymer segment A.

The block copolymer exhibiting the above-described DSC behavior or anyone polymer segment of the block copolymer may further satisfy thefollowing conditions.

For example, when the isotropic transition peak and the meltingtransition peak appear simultaneously, the difference (Ti−Tm) betweenthe temperature (Ti) at which the isotropic transition peak appears andthe temperature (Tm) at which the melting transition peak appears may bein a range of 5° C. to 70° C. In another example, the difference (Ti−Tm)may be 10° C. or more, 15° C. or more, 20° C. or more, 25° C. or more,30° C. or more, 35° C. or more, 40° C. or more, 45° C. or more, 50° C.or more, 55° C. or more, or 60° C. or more. The block copolymer having adifference (Ti−Tm) between the temperature (Ti) of the isotropictransition peak and the temperature (Tm) of the melting transition peakin the above range or the block copolymer comprising such a polymersegment can maintain excellent phase separation or self-assemblycharacteristics.

In another example, when the isotropic transition peak and the meltingtransition peak appear simultaneously, the ratio (M/I) of the area (I)of the isotropic transition peak and the area (M) of the meltingtransition peak may be in a range of 0.1 to 500. In the DSC analysis,the block copolymer having a ratio (M/I) of the area (I) of theisotropic transition peak and the area (M) of the melting transitionpeak in the above range or the block copolymer comprising such a polymersegment can maintain excellent phase separation or self-assemblycharacteristics. In another example, the ratio (M/I) may be 0.5 or more,1 or more, 1.5 or more, 2 or more, 2.5 or more, or 3 or more. In anotherexample, the ratio (M/I) may be 450 or less, 400 or less, 350 or less,300 or less, 250 or less, 200 or less, 150 or less, 100 or less, 90 orless, or 85 or less.

A method of performing the DSC analysis is known, and in the presentapplication, the above analysis can be performed by such a known method.

The temperature (Tm) range at which the melting transition peak appearsmay be a range of −10° C. to 55° C. In another example, the temperature(Tm) may be 50° C. or less, 45° C. or less, 40° C. or less, 35° C. orless, 30° C. or less, 25° C. or less, 20° C. or less, 15° C. or less,10° C. or less, 5° C. or less, or 0° C. or less.

The block copolymer may comprise a polymer segment having a side chain,as described below. In this case, the block copolymer may satisfyEquation 2 below.

10° C.≤Tm−12.25° C.×n+149.5° C.≤10° C.  [Equation 2]

In Equation 2, Tm is a temperature at which a melting transition peak ofthe block copolymer or the polymer segment having the side chainappears, and n is a number of chain-forming atoms of the side chain.

The block copolymer satisfying Equation above may have excellent phaseseparation or self-assembly properties.

In another example, Tm−12.25° C.×n+149.5° C. in Equation 2 may be −8° C.to 8° C., −6° C. to 6° C., or about −5° C. to 5° C. or so.

B. Condition 2

The block copolymer of the present application may comprise a polymersegment showing at least one peak in a predetermined range of thescattering vector (q) upon the XRD analysis (X-ray diffractionanalysis). The polymer segment satisfying Condition 2 may be the polymersegment A.

For example, any one polymer segment of the block copolymer may exhibitat least one peak in a scattering vector (q) range of 0.5 nm⁻¹ to 10nm⁻¹ in the X-ray diffraction analysis. In another example, thescattering vector (q) at which the peak appears may be 0.7 nm⁻¹ or more,0.9 nm⁻¹ or more, 1.1 nm⁻¹ or more, 1.3 nm⁻¹ or more, or 1.5 nm⁻¹ ormore. In another example, the scattering vector (q) at which the peakappears may be 9 nm⁻¹ or less, 8 nm⁻¹ or less, 7 nm⁻¹ or less, 6 nm⁻¹ orless, 5 nm⁻¹ or less, 4 nm⁻¹ or less, 3.5 nm⁻¹ or less, or 3 nm⁻¹ orless. The half-value width (full width at half maximum, FWHM) of thepeak identified in the above scattering vector (q) range may be in therange of 0.2 to 0.9 nm⁻¹. In another example, the half-value width maybe 0.25 nm⁻¹ or more, 0.3 nm⁻¹ or more, or 0.4 nm⁻¹ or more. In anotherexample, the half-value width may be 0.85 nm⁻¹ or less, 0.8 nm⁻¹ orless, or 0.75 nm⁻¹ or less.

In Condition 2, the term half-value width may mean a width of the peak(the difference in the scattering vector (q)) at a position showing the½ intensity of the maximum peak intensity.

The scattering vector (q) and the half-value width in the XRD analysisare values obtained by a numerical analytical method in which theresults obtained by the XRD analysis to be described below are appliedby a least-square method. In the method, the profile of the XRD patternsis subjected to Gaussian fitting in a state where a portion showing thesmallest intensity in the XRD diffraction patterns is taken as abaseline and the intensity in the above is set to zero, and then thescattering vector and the half-value width can be obtained from thefitted results. The R square at the time of Gaussian fitting is at least0.9 or more, 0.92 or more, 0.94 or more, or 0.96 or more. A methodcapable of obtaining the information as above from the XRD analysis isknown, and for example, a numerical analysis program such as origin canbe applied.

The polymer segment showing the peak of the half-value width in theabove scattering vector (q) range may comprise a crystalline sitesuitable for self-assembly. The block copolymer comprising the polymersegment identified in the above-described scattering vector (q) rangemay exhibit excellent self-assembly properties.

The XRD analysis can be performed by transmitting X-rays to a sample andthen measuring the scattering intensity according to the scatteringvector. The XRD analysis can be performed using a polymer prepared bypolymerizing only a monomer constituting any one polymer segment of theblock copolymer, for example, the polymer segment A. The XRD analysiscan be performed on such a polymer without any special pretreatment, andfor example, can be performed by drying the polymer under appropriateconditions and then passing it through X-rays. As the X-ray, an X-rayhaving a vertical size of 0.023 mm and a horizontal size of 0.3 mm canbe applied. The scattering vector and the half-value width can beobtained by obtaining as an image 2D diffraction patterns that arescattered in the sample and exited using a measuring instrument (forexample, 2D marCCD), and fitting the obtained diffraction pattern withthe above-described manner.

C. Condition 3

The block copolymer of the present application may comprise, as thepolymer segment A, a polymer segment having a side chain to be describedbelow, wherein the number (n) of chain-forming atoms of the side chaincan satisfy Equation 1 below with the scattering vector (q) obtained bythe X-ray diffraction analysis performed in the same manner as inCondition 2 above.

3 nm⁻¹ to 5 nm⁻¹ =nq/(2×π)  [Equation 1]

In Equation 1, n is a number of the chain-forming atoms, and q is thesmallest scattering vector (q) in which the peak is observed in theX-ray diffraction analysis for the polymer segment containing the sidechain, or the scattering vector (q) in which the peak of the largestpeak area is observed. Also, in Equation 1, π means the circularconstant.

The scattering vector or the like introduced into Equation 1 is a valueobtained by the same manner mentioned in the above-described X-raydiffraction analysis method.

The scattering vector (q) introduced in Equation 1 may be, for example,a scattering introduced into Equation 1 may be 0.7 nm⁻¹ or more, 0.9nm⁻¹ or more, 1.1 nm⁻¹ or more, 1.3 nm⁻¹ or more, or 1.5 nm⁻¹ or more.In another example, the scattering vector (q) introduced into Equation 1above may be 9 nm⁻¹ or less, 8 nm⁻¹ or less, 7 nm⁻¹ or less, 6 nm⁻¹ orless, 5 nm⁻¹ or less, 4 nm⁻¹ or less, 3.5 nm⁻¹ or less, or 3 nm⁻¹ orless.

When a polymer composed of only the polymer segment comprising the sidechain of the block copolymer has formed a film, Equation 1 shows arelationship of the distance (D) between the polymer main chainscontaining the side chains and the number of chain-forming atoms in theside chain, and when the number of chain-forming atoms of the side chainin the polymer having the side chain satisfies Equation 1 above, thecrystallinity represented by the side chain is increased, whereby thephase separation property or the vertical orientation can besignificantly improved. In another example, the nq/(2×π) according toEquation 1 above may also be 4.5 nm⁻¹ or less. Here, the distance (D,unit: nm) between the polymer main chains in which the side chains arecontained can be calculated by the equation D=2×π/q, where D is thedistance (D, unit: nm), and it and q are as defined in Equation 1.

D. Condition 4

The absolute value of the difference between the surface energy of thepolymer segment A and the surface energy of the polymer segment B in theblock copolymer of the present application may be 10 mN/m or less, 9mN/m or less, 8 mN/m or less, 7.5 mN/m or less, or 7 mN/m or less. Theabsolute value of the difference in surface energy may be 1.5 mN/m, 2mN/m or 2.5 mN/m or more. The structure in which the polymer segments Aand B having the absolute value of the difference in surface energy inthis range are connected by covalent bonds can induce effectivemicrophase separation. Here, the polymer segment A may be, for example,a polymer segment having a side chain as described below.

The surface energy can be measured using a drop shape analyzer (DSA100product from KRUSS). Specifically, the surface energy can be measuredfor a film in which a coating liquid obtained by diluting a targetsample (block copolymer or homopolymer), which is measured, influorobenzene to a solid concentration of about 2 wt %, is coated on asubstrate to a thickness of about 50 nm and a coating area of 4 cm²(width: 2 cm, height: 2 cm), and dried at room temperature for about 1hour, and then subjected to thermal annealing at 160° C. for about 1hour. The process of dropping the deionized water whose surface tensionis known on the film subjected to the thermal annealing and obtainingthe contact angle thereof is repeated five times to obtain an averagevalue of the obtained five contact angle values, and identically, theprocess of dropping the diiodomethane whose surface tension is knownthereon and obtaining the contact angle thereof is repeated five timesto obtain an average value of the obtained five contact angle values.Then, the surface energy can be obtained by substituting the value(Strom value) regarding the solvent surface tension by theOwens-Wendt-Rabel-Kaelble method using the obtained average values ofthe contact angles for the deionized water and diiodomethane. Thenumerical value of the surface energy for each polymer segment of theblock copolymer can be obtained for a homopolymer made of only themonomer forming the polymer segment by the above-described method.

When the block copolymer comprises the above-described side chain, thepolymer segment comprising the side chain may have a higher surfaceenergy than the other polymer segment. For example, if the polymersegment A of the block copolymer comprises the side chain, the polymersegment A may have a higher surface energy than the polymer segment B.In this case, the surface energy of the polymer segment A may be in arange of about 20 mN/m to 40 mN/m. The surface energy of the polymersegment A may be 22 mN/m or more, 24 mN/m or more, 26 mN/m or more, or28 mN/m or more. The surface energy of the polymer segment A may be 38mN/m or less, 36 mN/m or less, 34 mN/m or less, or 32 mN/m or less. Theblock copolymer comprising such a polymer segment A and exhibiting adifference in surface energy from the polymer segment B as above canexhibit excellent self-assembly properties.

E. Condition 5

The absolute value of the difference in density between the polymersegment A and the polymer segment B in the block copolymer may be 0.25g/cm³ or more, 0.3 g/cm³ or more, 0.35 g/cm³ or more, 0.4 g/cm³ or more,or 0.45 g/cm³ or more. The absolute value of the difference in densitymay be 0.9 g/cm³ or more, 0.8 g/cm³ or less, 0.7 g/cm³ or less, 0.65g/cm³ or less, or 0.6 g/cm³ or less. The structure in which the polymersegment A and the polymer segment B having the absolute value of thedensity difference in this range are linked by covalent bonds can induceeffective microphase separation by phase separation due to propernon-compatibility.

The density of each polymer segment in the block copolymer can bemeasured using a known buoyancy method, and for example, the density canbe measured by analyzing the mass of the block copolymer in a solvent,such as ethanol, which is known in mass and density in air.

When the above-described side chain is included, the polymer segmentcomprising the side chain may have a lower density than the otherpolymer segment. For example, if the polymer segment A of the blockcopolymer comprises the side chain, the polymer segment A may have alower density than the polymer segment B. In this case, the density ofthe polymer segment A may be in a range of about 0.9 g/cm³ to 1.5 g/cm³or so. The density of the polymer segment A may be 0.95 g/cm³ or more.The density of the polymer segment A may be 1.4 g/cm³ or less, 1.3 g/cm³or less, 1.2 g/cm³ or less, 1.1 g/cm³ or less, or 1.05 g/cm³ or less.The block copolymer comprising such a polymer segment A and exhibiting adensity difference with the polymer segment B as above can exhibitexcellent self-assembly properties.

As described above, the block copolymer may satisfy any one of the aboveconditions, or may satisfy two or more selected from them.

In one example, the block copolymer may comprise a polymer segment Asatisfying any one or two or more of Conditions 1 to 3 among the aboveconditions and a polymer segment B having a difference in surface energyaccording to Condition 4 above.

Although not limited by theory, the polymer segment A satisfying any oneof Conditions 1 to 3 can exhibit crystallinity or liquid crystallinity,and accordingly, it can be packed with regularity upon forming theself-assembled structure. In this state, when the polymer segment A andthe polymer segment B satisfy the difference in surface energy accordingto Condition 4, the domains formed by the respective polymer segments Aand B are substantially neutralized, whereby the film can be orientedvertically in the structure of the above-mentioned laminate even ifthere is no neutral treatment region.

In the block copolymer, the volume fraction of the polymer segment A maybe in a range of 0.4 to 0.8, and the volume fraction of the polymersegment B may be in a range of 0.2 to 0.6. The sum of the volumefractions of the polymer segments A and B may be 1. In another example,the volume fraction of the polymer segment A may be about 0.75 or less,about 0.7 or less, about 0.65 or less, about 0.6 or less, about 0.55 orless, or about 0.5 or less. Also, the volume fraction of the polymersegment B may be about 0.25 or more, about 0.3 or more, about 0.35 ormore, about 0.4 or more, about 0.45 or more, or about 0.5 or more. Theblock copolymer comprising each of the above-mentioned segments at theabove volume fractions may exhibit excellent self-assembly properties inthe laminate. The volume fraction of each block in the block copolymercan be determined based on the density and the molecular weight measuredby GPC (gel permeation chromatography), of each block.

As other conditions, the block copolymer may have a number averagemolecular weight (Mn) in a range of, for example, 3,000 to 300,000. Inthis specification, the term number average molecular weight is aconverted value for standard polystyrene measured using GPC (gelpermeation chromatograph), and the term molecular weight herein means anumber average molecular weight, unless otherwise specified. Unlessotherwise specified, the unit of number average molecular weight is alsog/mol. In another example, the molecular weight (Mn) may be, forexample, 3000 or more, 5000 or more, 7000 or more, 9000 or more, 11000or more, 13000 or more, or 14000 or more. In another example, themolecular weight (Mn) may be 250000 or less, 200000 or less, 180000 orless, 160000 or less, 140000 or less, 120000 or less, 90000 or less,80000 or less, 70000 or less, 60,000 or less, 50000 or less, 40000 orless, 30000 or less, 25000 or less, 20000 or less, or 15000 or less. Theblock copolymer may have a polydispersity (Mw/Mn) in a range of 1.01 to1.60. In another example, the polydispersity may be about 1.1 or more,about 1.2 or more, about 1.3 or more, or about 1.4 or more.

In this range, the block copolymer may exhibit proper self-assemblyproperties. The number average molecular weight of the block copolymeror the like can be adjusted in consideration of the desiredself-assembled structure and the like.

The above-mentioned conditions can be achieved, for example, bycontrolling the structure of the block copolymer. For example, thepolymer segment A of the block copolymer satisfying one or more of theabove-mentioned conditions may comprise the side chain to be describedbelow. The polymer segment A may comprise a ring structure, where theside chain may be substituted on the ring structure. The side chain maybe directly substituted on the ring structure or may be substituted viaa suitable linker. The ring structure may be an aromatic structure or analicyclic ring structure as described above. No halogen atom may bepresent in such a ring structure. The polymer segment B contained in theblock copolymer together with the polymer segment A may comprise 3 ormore halogen atoms. At this time, the polymer segment B may comprise aring structure, where the halogen atoms may be substituted on the ringstructure. The ring structure may be an alicyclic ring structure or anaromatic structure as described above.

Here, the aromatic structure or the alicyclic ring structure may be astructure contained in the main chain of the polymer segment, or may bea structure linked to the polymer segment main chain in a side chainform.

In one example, the block copolymer satisfying one or more of the aboveconditions may comprise a polymer segment A comprising a side chain anda polymer segment B different therefrom. Here, the side chain may be aside chain having 8 or more chain-forming atoms, as described below. Thepolymer segment A may be a polymer segment satisfying any one of theabove-described conditions 1 to 3, satisfying two or more of theforegoing, or satisfying all of the above conditions.

Here, the term side chain means a chain connected to the main chain ofthe polymer, and the term chain-forming atom is an atom forming the sidechain, which means an atom forming the straight chain structure of thechain. The side chain may be linear or branched, but the number ofchain-forming atoms is calculated by only the number of atoms formingthe longest straight chain, where other atoms bonded to thechain-forming atoms (for example, when the chain-forming atom is acarbon atom, hydrogen atoms bonding to the carbon atom, etc.) are notincluded in the calculation. For example, in the case of a side chain,the number of chain-forming atoms can be calculated as the number ofchain-forming atoms forming the longest chain moiety. For example, whenthe side chain is an n-pentyl group, all of the chain-forming atoms arecarbon atoms and the number thereof is 5, and even when the side chainis a 2-methylpentyl group, all of the chain-forming atoms are carbonatoms and the number thereof is 5. The chain-forming atom may beexemplified by carbon, oxygen, sulfur or nitrogen, and the like, and theappropriate chain-forming atom may be carbon, oxygen or nitrogen, or maybe carbon or oxygen. The number of chain-forming atoms may be 8 or more,9 or more, 10 or more, 11 or more, or 12 or more. The number of thechain-forming atoms may be 30 or less, 25 or less, 20 or less, or 16 orless.

For the control of the above-described conditions, the polymer segment Aof the block copolymer may have a chain with 8 or more chain-formingatoms connected to the side chain. In this specification, the term chainand side chain may refer to the object identical to each other.

The side chain may be a chain comprising 8 or more, 9 or more, 10 ormore, 11 or more, or 12 or more chain-forming atoms, as mentioned above.Also, the number of the chain-forming atoms may be 30 or less, 25 orless, 20 or less, or 16 or less. The chain-forming atom may be a carbon,oxygen, nitrogen or sulfur atom and may suitably be carbon or oxygen.

As the side chain, a hydrocarbon chain such as an alkyl group, analkenyl group or an alkynyl group can be exemplified. At least one ofthe carbon atoms of the hydrocarbon chain may be replaced by a sulfuratom, an oxygen atom or a nitrogen atom.

When the side chain is connected to the ring structure, the chain may bedirectly connected to the ring structure or may be connected via alinker. The linker may be exemplified by an oxygen atom, a sulfur atom,—NR₁—, —S(═O)₂—, a carbonyl group, an alkylene group, an alkenylenegroup, an alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—. Here, R₁ may behydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxygroup or an aryl group, and X₁ may be a single bond, an oxygen atom, asulfur atom, —NR₂—, —S(═O)₂—, an alkylene group, an alkenylene group oran alkynylene group, where R₂ may be hydrogen, an alkyl group, analkenyl group, an alkynyl group, an alkoxy group or an aryl group. Thesuitable linker may be exemplified by an oxygen atom. The side chain maybe connected to a ring structure such as an aromatic structure, forexample, via an oxygen atom or a nitrogen atom.

When the ring structure such as the aromatic structure described aboveis connected to the main chain of the polymer segment in a side chainform, the aromatic structure may also be directly connected to the mainchain or may be connected via a linker. In this case, the linker can beexemplified by an oxygen atom, a sulfur atom, —S(═O)₂—, a carbonylgroup, an alkylene group, an alkenylene group, an alkynylene group,—C(═O)—X₁— or —X₁—C(═O)—, where X₁ may be a single bond, an oxygen atom,a sulfur atom, —S(═O)₂—, an alkylene group, an alkenylene group or analkynylene group. The suitable linker connecting the aromatic structureto the main chain can be exemplified by —C(═O)—O— or —O—C(═O)—, but isnot limited thereto.

In another example, the ring structure such as the aromatic structurecontained in the polymer segment B of the block copolymer may comprise 1or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms.The number of halogen atoms may be, for example, 30 or less, 25 or less,20 or less, 15 or less, or 10 or less. The halogen atom may beexemplified by fluorine or chlorine, and the like, and the use of afluorine atom may be advantageous. As described above, the polymersegment having a ring structure such as an aromatic structure containinga halogen atom can efficiently realize a phase separation structurethrough proper interaction with other polymer segments.

Here, the polymer segment A may be, for example, a polymer segmentcomprising a unit represented by Formula 1 below. The polymer segmentmay be a polymer segment containing a unit of Formula 1 below as a maincomponent. In this specification, the fact that any polymer segmentcomprises a certain unit as a main component may mean a case where thepolymer segment comprises the unit 60% or more, 70% or more, 80% ormore, 90% or more, or 95% or more by weight, or a case where itcomprises the unit 60 mol % or more, 70 mol % or more, 80 mol % or more,90 mol % or more, or 95 mol % or more.

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbonatoms, X is a single bond, an oxygen atom, a sulfur atom, —S(═O)₂—, acarbonyl group, an alkylene group, an alkenylene group, an alkynylenegroup, —C(═O)—X₁— or —X₁—C(═O)—, where X₁ is an oxygen atom, a sulfuratom, —S(═O)₂—, an alkylene group, an alkenylene group or an alkynylenegroup, and Y is a monovalent substituent comprising a ring structure towhich the side chain having 8 or more chain-forming atoms is linked.

When the side chain is an alkyl group, the alkyl group may contain 8 ormore, 9 or more, 10 or more, 11 or more, or 12 or more carbon atoms,where the number of carbon atoms of this alkyl group may be 30 or less,25 or less, 20 or less, or 16 or less. Also, when the side chain is analkenyl group or alkynyl group, it may contain 8 or more, 9 or more, 10or more, 11 or more, or 12 or more carbon atoms, where the number ofcarbon atoms of this alkenyl group or alkynyl group may be 30 or less,25 or less, 20 or less, or 16 or less.

In another example, X of Formula 1 may be —C(═O)O— or —OC(═O)—.

In Formula 1, Y is a substituent comprising the above-described sidechain, which may be, for example, a substituent containing an aromaticstructure having 6 to 18 carbon atoms or 6 to 12 carbon atoms. Here, thechain may be, for example, a linear alkyl group containing 8 or more, 9or more, 10 or more, 11 or more, or 12 or more carbon atoms. This alkylgroup may contain 30 or less, 25 or less, 20 or less, or 16 or lesscarbon atoms. Such a chain may be linked to the aromatic structuredirectly or via the above-mentioned linker.

In another example, the unit of Formula 1 above in the polymer segment Amay be a unit of Formula 2 below.

In Formula 2, R is hydrogen or an alkyl group having 1 to 4 carbonatoms, X is —C(═O)—O—, P is an arylene group having 6 to 12 carbonatoms, Q is an oxygen atom, and Z is the side chain having 8 or morechain-forming atoms.

In another example, P in Formula 2 may be phenylene, and in anotherexample, Z may be a linear alkyl group having 9 to 20 carbon atoms, 9 to18 carbon atoms, 9 to 16 carbon atoms, 10 to 16 carbon atoms, 11 to 16carbon atoms or 12 to 16 carbon atoms. Here, when P is phenylene, Q maybe connected to the para position of the phenylene. Here, the alkylgroup, arylene group, phenylene group and side chain may be optionallysubstituted with one or more substituents.

The polymer segment B of the block copolymer may be, for example, apolymer segment containing a unit represented by Formula 3 below. Thepolymer segment may comprise a unit of Formula 3 below as a maincomponent.

In Formula 3, X₂ is a single bond, an oxygen atom, a sulfur atom,—S(═O)₂—, an alkylene group, an alkenylene group, an alkynylene group,—C(═O)—X₁— or —X₁—C(═O)—, where X₁ is a single bond, an oxygen atom, asulfur atom, —S(═O)₂—, an alkylene group, an alkenylene group or analkynylene group, and W is an aryl group containing at least one halogenatom.

In another example, X₂ of Formula 3 may be a single bond or an alkylenegroup.

In Formula 3, the aryl group of W may be an aryl group having 6 to 12carbon atoms or a phenyl group, and this aryl group or phenyl group maycontain 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogenatoms. Here, the number of halogen atoms may be, for example, 30 orless, 25 or less, 20 or less, 15 or less, or 10 or less. As the halogenatom, a fluorine atom may be exemplified.

In another example, the unit of Formula 3 may be represented by Formula4 below.

In Formula 4, X₂ is a single bond, an oxygen atom, a sulfur atom,—S(═O)₂—, an alkylene group, an alkenylene group, an alkynylene group,—C(═O)—X₁— or —X₁—C(═O)—, where X₁ is a single bond, an oxygen atom, asulfur atom, —S(═O)₂—, an alkylene group, an alkenylene group or analkynylene group, R₁ to R₅ are each independently hydrogen, an alkylgroup, a haloalkyl group or a halogen atom, and the number of halogenatoms contained in R₁ to R₅ is 1 or more.

In Formula 4, R₁ to R₅ may be each independently a hydrogen atom, analkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to4 carbon atoms or halogen, where halogen may be chlorine or fluorine.

In Formula 4, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or moreof R₁ to R₅ may contain halogen. The upper limit of the halogen numberis not particularly limited and may be, for example, 12 or less, 8 orless, or 7 or less.

As described above, the block copolymer may be a diblock copolymercomprising any two of the above units, or may be a block copolymercomprising any one or both of the two polymer segments together withother polymer segments.

The method of producing such a block copolymer is not particularlylimited. The block copolymer may be polymerized by, for example, an LRP(Living Radical Polymerization) method, and an example thereof includesanionic polymerization in which the block copolymer is synthesized inthe presence of an inorganic acid salt such as an alkali metal or analkali earth metal by using an organic rare earth metal complex as apolymerization initiator or by using an organic alkali metal compound asa polymerization initiator, an anionic polymerization method in whichthe block copolymer is synthesized in the presence of an organicaluminum compound by using an organic alkali metal compound as apolymerization initiator, an atom transfer radical polymerization method(ATRP) using an atom transfer radical polymerization agent as apolymerization inhibitor, an ARGET (Activators Regenerated by ElectronTransfer) atom transfer radical polymerization method (ATRP), which usesan atom transfer radical polymerization agent as a polymerizationinitiator, but performs polymerization under an organic or inorganicreducing agent that generates electrons, an ICAR (Initiators forContinuous Activator Regeneration) atom transfer radical polymerizationmethod (ATRP), a polymerization method by reversibleaddition-fragmentation chain transfer (RAFT) using an inorganic reducingagent and a reversible addition-fragmentation chain transfer agent or amethod of using an organotellurium compound as an initiator, and thelike, and a suitable method may be selected among these methods andapplied.

For example, the block copolymer can be prepared in a manner comprisingpolymerizing a reactant comprising monomers capable of forming thepolymer segments in the presence of a radical initiator and a livingradical polymerization reagent by a living radical polymerizationmethod. The process of producing the polymer segment copolymer mayfurther comprise, for example, a process of precipitating thepolymerization product produced through the above processes in anon-solvent.

The kind of the radical initiator is not particularly limited, which maybe appropriately selected in consideration of polymerization efficiency,and for example, an azo compound such as AIBN (azobisisobutyronitrile)or 2,2′-azobis-(2,4-dimethylvaleronitrile), or peroxide series such asBPO (benzoyl peroxide) or DTBP (di-t-butyl peroxide) may be used.

The living radical polymerization process may be performed in a solventsuch as, for example, methylene chloride, 1,2-dichloroethane,chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform,tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylformamide,dimethyl sulfoxide or dimethylacetamide.

As the non-solvent, an alcohol such as methanol, ethanol, normalpropanol or isopropanol, a glycol such as ethylene glycol, n-hexane,cyclohexane, n-heptane or ether series such as petroleum ether can beused, without being limited thereto.

On the other hand, in the laminate, the polymer forming the stripepattern may be a polymer satisfying any one or two or more of Conditions1 to 3 above, or may be a polymer in which the absolute value of thedifference in surface energy between the polymer segment A and thepolymer segment A is 10 mN/m or less. Here, the difference in surfaceenergy may be 9 mN/m or less, 8 mN/m or less, 7.5 mN/m or less, or 7mN/m or less. The absolute value of the difference in surface energy maybe 1.5 mN/m, 2 mN/m or 2.5 mN/m or more.

As the above-mentioned stripe pattern is formed by applying such apolymer, the block copolymer in the laminate can more effectivelyrealize the self-assembled structure. The kind of the polymer is notparticularly limited. For example, the polymer satisfying any one or twoor more of Conditions 1 to 3 above may be the above-mentioned polymersegment A, and the polymer, in which the absolute value of thedifference in surface energy with the polymer segment A is 10 mN/m orless, may be the above-mentioned polymer segment B. Therefore, thepolymer may be a polymer containing the above-described unit of Formula1 or 2 as a main component, or may be a polymer containing theabove-described unit of Formula 3 or 4 as a main component.

In one example, the polymer forming the polymer stripe pattern may havea molecular weight (Mn (Number Average Molecular Weight)), for example,in a range of 8,000 to 100,000. Under such a range, desired excellentresults can be ensured.

The present application also relates to a method for producing apatterned substrate using such a laminate. The patterned substrate thusproduced may be used for various electric or electronic elements, aprocess of forming the pattern, a recording medium such as a magneticstorage medium and a flash memory, or a biosensor, and the like.

The production method may comprise a step of coating a coating liquidcomprising a block copolymer, which comprises a polymer segment Asatisfying one or more of Conditions 1 to 3 above and a polymer segmentB having an absolute value of a difference in surface energy with thepolymer segment A of 10 mN/m or less, on the polymer stripe pattern ofthe substrate that the polymer stripe pattern is formed on its surface,and forming a self-assembled structure of the block copolymer.

As described above, the polymer of the polymer stripe pattern may be apolymer which satisfies one or more of Conditions 1 to 3 above, or hasan absolute value of the difference in surface energy with the polymersegment A of 10 mN/m or less.

Here, the method of forming the stripe pattern on the substrate is notparticularly limited. For example, the pattern may be produced by amethod comprising steps of: (1) forming a polymer film on a substrate;(2) forming a resist film on the polymer film and patterning the resistfilm; and (3) etching the polymer film using the patterned resist filmas a mask.

Here, the polymer film may be formed using the above-described polymer,that is, the polymer containing the above-described unit of Formula 1 or2 as a main component, or the polymer containing the above-describedunit of Formula 3 or 4 as a main component.

Upon forming such a polymer film, for example, a step of coating apolymer film and holding the relevant polymer film at a temperature in arange of about 100° C. to 300° C. for about 1 minute to 100 minutes mayalso be performed.

Here, an antireflection layer may be formed between the polymer film andthe resist film. The antireflection layer may be formed of SiARC using,for example, a silicon material (Si), and in addition to this, all otherknown materials may be applied. The antireflection layer may be formedby a known coating or vapor deposition method.

The resist film may be formed using a known material, for example, amaterial that can be patterned by a known lithographic process. Such aresist film can be patterned by a known lithographic process, and theresist film thus patterned can be applied as a mask in the subsequentprocess of forming a polymer stripe pattern. The patterning of theresist film can be performed so that the dimensions of the polymerstripe pattern can be adjusted to a desired level in a subsequentetching process.

Following the patterning of the resist film, an etching process in whichthe patterned resist film is applied as an etch mask can be performed.In this etching process, the polymer film and the antireflection layerin the region excluding the region protected by the etch mask can beetched. This etching can be performed by a known etching method, and forexample, can be performed by an RIE (reactive ion etching) method. Theabove-described polymer stripe pattern can be formed by this etching.The etching may also be performed until the polymer film of the regionnot protected by the etch mask is all removed, or may be formed so as toleave a part of the polymer film.

After the polymer stripe pattern is formed in the above-describedmanner, the resist film can be removed in a known manner.

The method of forming the polymer film comprising the block copolymer onthe substrate that the polymer pattern is formed in the above manner andforming the self-assembled structure of the block copolymer in thepolymer film is not particularly limited.

For example, the method may comprise a process of coating the blockcopolymer or a coating liquid comprising the same to form a layer andannealing the layer. Here, the annealing process may be a thermalannealing process or a solvent annealing process.

The thermal annealing may be performed based on, for example, the phasetransition temperature or the glass transition temperature of the blockcopolymer, and may be performed at, for example, a temperature above theglass transition temperature or the phase transition temperature. Thetime for which this thermal annealing is performed is not particularlylimited, and the treatment can be performed within a range of, forexample, about 1 minute to 72 hours, but the time can be changed asneeded. In the thermal annealing process, the heat treatment temperaturemay be, for example, about 100° C. to 250° C., but this may be changedin consideration of the block copolymer to be used. In addition, thesolvent annealing process may also be performed in an appropriatenon-polar solvent and/or polar solvent at room temperature for about 1minute to 72 hours.

The method for producing a patterned substrate may further perform astep of selectively removing any one polymer segment of the blockcopolymer in which the self-assembly structure is formed as above.

For example, it may comprise a process of selectively removing thepolymer segment A or B of the block copolymer in the laminate. Theproduction method may comprise selectively removing one or more polymersegments of the block copolymer, and then etching the substrate. In thisway, it is possible to form, for example, a nanoscale fine pattern. Inaddition, various types of patterns such as nano-rods or nano-holes canbe formed through the above-described method depending on the shape ofthe block copolymer in the polymer film. If necessary, a copolymerdifferent from the block copolymer or a homopolymer, and the like may bemixed for pattern formation.

The method of selectively removing any one polymer segment of the blockcopolymer in the above method is not particularly limited, and forexample, a method of removing a relatively soft polymer segment byirradiating the polymer film with an appropriate electromagnetic wave,for example, ultraviolet or the like, can be used. In this case, theultraviolet irradiation condition is determined according to the type ofthe polymer segment of the block copolymer, and the method can beperformed, for example, by being irradiated with ultraviolet having awavelength of about 254 nm for 1 minute to 60 minutes.

Following the ultraviolet irradiation, a step of treating the polymerfilm with an acid or the like to further remove the segment decomposedby ultraviolet may also be performed.

The step of etching the substrate using the polymer film in which thepolymer segments are selectively removed as a mask is not particularlylimited, which may be performed, for example, through a reactive ionetching step using CF₄/Ar ions or the like and following this process, astep of removing the polymer film from the substrate by an oxygen plasmatreatment or the like may also be performed.

Advantageous Effects

The present application can provide a laminate which is capable offorming a highly aligned block copolymer on a substrate and thus can beeffectively applied to production of various patterned substrates, and amethod for producing a patterned substrate using the same.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram of a polymer stripe pattern of the presentapplication.

FIG. 2 is a view showing the analysis results of GIWAXS.

FIGS. 3 to 7 are photographs showing the results of Examples orComparative Examples.

MODE FOR INVENTION

Hereinafter, the present application will be described in detail by wayof examples according to the present application and comparativeexamples, but the scope of the present application is not limited by thefollowing examples.

1. NMR Measurement

NMR analyses were performed at room temperature using an NMRspectrometer including a Varian Unity Inova (500 MHz) spectrometer witha triple resonance 5 mm probe. The analytes were diluted in a solventfor NMR measurement (CDCl₃) to a concentration of about 10 mg/ml, andchemical shifts were expressed in ppm.

<Application Abbreviation>

br=broad signal, s=singlet, d=doublet, dd=double doublet, t=triplet,dt=double triplet, q=quartet, p=quintet, m=multiplet.

2. GPC (Gel Permeation Chromatograph)

The number average molecular weight (Mn) and the molecular weightdistribution were measured using GPC (gel permeation chromatography).Into a 5 mL vial, an analyte such as block copolymers of Examples orComparative Examples or a giant initiator is put and diluted in THF(tetrahydrofuran) to be a concentration of about 1 mg/mL or so. Then, astandard sample for calibration and a sample to be analyzed werefiltered through a syringe filter (pore size: 0.45 μm) and thenmeasured. As the analytical program, ChemStation from AgilentTechnologies was used, and the elution time of the sample was comparedwith the calibration curve to obtain the weight average molecular weight(Mw) and the number average molecular weight (Mn), respectively, and themolecular weight distribution (PDI) was calculated by the ratio (Mw/Mn)thereof. The measurement conditions of GPC are as follows.

<GPC Measurement Condition>

Instrument: 1200 series from Agilent Technologies

Column: using two PLgel mixed B from Polymer Laboratories

Solvent: THF

Column temperature: 35° C.

Sample concentration: 1 mg/mL, 200 L injection

Standard sample: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400,7200, 3940, 485)

3. GISAXS (Grazing Incidence Small Angle X-Ray Scattering)

The grazing incidence small angle X-ray scattering (GISAXS) analysis wasperformed using a Pohang accelerator 3C beamline. The block copolymer tobe analyzed was diluted in fluorobenzene to a solid concentration ofabout 0.7 wt % to prepare a coating liquid, and the coating liquid wasspin-coated on a base material to a thickness of about 5 nm. The coatingarea was adjusted to 2.25 cm² or so (width: 1.5 cm, height: 1.5 cm). Thecoated polymer film was dried at room temperature for about 1 hour andthermally annealed again at about 160° C. for about 1 hour to induce aphase separation structure. Subsequently, a film, in which the phaseseparation structure was formed, was formed. After an X-ray was incidenton the film at an incident angle in a range of about 0.12 degrees to0.23 degrees corresponding to the angle between the critical angle ofthe film and the critical angle of the base material, an X-raydiffraction pattern, which was scattered from the film to a detector (2DmarCCD) and exited, was obtained. At this time, the distance from thefilm to the detector was selected as such a range that the self-assemblypattern formed on the film was well observed within a range of about 2 mto 3 m. As the base material, a base material having a hydrophilicsurface (a silicon substrate treated with a piranha solution and havinga room temperature wetting angle of about 5 degrees to pure water) or abase material having a hydrophobic surface (a silicon substrate treatedwith HMDS (hexamethyldisilazane) and having a room temperature wettingangle of about 60 degrees to pure water) was used.

4. XRD Analysis Method

The XRD analysis was performed by transmitting X rays to a sample at aPohang accelerator 4C beamline to measure the scattering intensityaccording to the scattering vector (q). As the sample, a polymer in apowder state dried by purifying a synthesized polymer without specialpretreatment and then maintaining it in a vacuum oven for one day or so,was placed in a cell for XRD measurement and used. Upon the XRD patternanalysis, an X-ray with a vertical size of 0.023 mm and a horizontalsize of 0.3 mm was used and a 2D marCCD was used as a detector. A 2Ddiffraction pattern scattered and exited was obtained as an image. Theobtained diffraction pattern was analyzed by a numerical analyticalmethod to which a least-square method was applied to obtain informationsuch as a scattering vector and a half-value width. Upon the analysis,an origin program was applied, and the profile of the XRD patterns wassubjected to Gaussian fitting in a state where a portion showing thesmallest intensity in the XRD diffraction patterns was taken as abaseline and the intensity in the above was set to zero, and then thescattering vector and the half-value width were obtained from the fittedresults. The R square was set to be at least 0.96 or more upon Gaussianfitting.

5. Measurement of Surface Energy

The surface energy was measured using a drop shape analyzer (DSA100product from KRUSS). A coating liquid was prepared by diluting thesubstance (polymer), which is measured, in fluorobenzene to a solidconcentration of about 2 wt %, and the prepared coating liquid wasspin-coated on a silicon wafer to a thickness of about 50 nm and acoating area of 4 cm² (width: 2 cm, height: 2 cm). The coating layer wasdried at room temperature for about 1 hour and then subjected to thermalannealing at about 160° C. for about 1 hour. The process of dropping thedeionized water whose surface tension was known on the film subjected tothermal annealing and obtaining the contact angle thereof was repeatedfive times to obtain an average value of the obtained five contact anglevalues. In the same manner, the process of dropping the diiodomethanewhose surface tension was known thereon and obtaining the contact anglethereof was repeated five times to obtain an average value of theobtained five contact angle values. The surface energy was obtained bysubstituting the value (Strom value) regarding the solvent surfacetension by the Owens-Wendt-Rabel-Kaelble method using the obtainedaverage values of the contact angles for the deionized water anddiiodomethane. The numerical value of the surface energy for eachpolymer segment of the block copolymer was obtained for a homopolymermade of only the monomer forming the polymer segment by theabove-described method.

6. GIWAXS (Grazing Incidence Wide Angle X-Ray Scattering)

The grazing incidence wide angle X-ray scattering (GIWAXS) analysis wasperformed using a Pohang accelerator 3C beamline. The homopolymer to beanalyzed was diluted in toluene to a solid concentration of about 1 wt %to prepare a coating liquid, and the coating liquid was spin-coated on abase material to a thickness of about 30 nm. The coating area wasadjusted to about 2.25 cm² (width: 1.5 cm, height: 1.5 cm). The coatedpolymer film was dried at room temperature for about 1 hour and thensubjected to thermal annealing at a temperature of about 160° C. forabout 1 hour to form a film. After an X-ray was incident on the film atan incident angle in a range of about 0.12 degrees to 0.23 degreescorresponding to the angle between the critical angle of the film andthe critical angle of the base material, an X-ray diffraction pattern,which was scattered from the film to a detector (2D marCCD) and exited,was obtained. At this time, the distance from the film to the detectorwas selected as such a range that the crystal or liquid crystalstructure formed on the film was well observed within a range of about0.1 m to 0.5 m. As the base material, a silicon substrate treated with apiranha solution and having a room temperature wetting angle of about 5degrees to pure water was used. In the GIWAXS spectrum, the scatteringintensity in the azimuthal angle range of −90 degrees to 90 degrees ofthe diffraction pattern in the range of 12 nm⁻¹ to 16 nm⁻¹ (azimuthalangle when the upward direction of the diffraction pattern (out-of-planediffraction pattern) is set as 0 degrees) was plotted, and thehalf-value width was obtained from the graph through Gauss fitting.Furthermore, when half of the peak was observed upon Gauss fitting,twice the value of the obtained half-value width (FWHM) was defined asthe half-value width of the peak.

7. DSC Analysis

The DSC analysis was performed using PerkinElmer DSC800 equipment. Usingthe equipment, it was performed by a method in which the sample to beanalyzed was heated at a speed of 10° C. per minute from 25° C. to 200°C., cooled again at a speed of −10° C. per minute from 200° C. to −80°C., and raised at a speed of 10° C. per minute from −80° C. to 200° C.under a nitrogen atmosphere to obtain an endothermic curve. The obtainedendothermic curve was analyzed to obtain a temperature (meltingtransition temperature, Tm) indicating a melting transition peak or atemperature (isotropic transition temperature, Ti) indicating anisotropic transition peak, and the area of the peak was obtained. Here,the temperature was defined as the temperature corresponding to the apexof each peak. The area per unit mass of each peak is defined as thevalue obtained by dividing the area of each peak by the mass of thesample, and this calculation can be calculated using the programprovided by the DSC equipment.

Preparation Example 1. Synthesis of Monomer (A)

A monomer (DPM-C12) of Formula A below was synthesized in the followingmanner. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g,94.2 mmol) were placed in a 250 mL flask, dissolved in 100 mL ofacetonitrile, and then an excess amount of potassium carbonate was addedthereto and reacted at 75° C. for about 48 hours under a nitrogencondition. After the reaction, the remaining potassium carbonate wasfiltered off and the acetonitrile used in the reaction was also removed.A mixed solvent of DCM (dichloromethane) and water was added thereto towork up the mixture, and the separated organic layers were collected andpassed through MgSO₄ to be dehydrated. Subsequently, the target product(4-dodecyloxyphenol) (9.8 g, 35.2 mmol) in a white solid phase wasobtained in a yield of about 37% using dichloromethane in columnchromatography.

<NMR Analysis Result>

¹H-NMR (CDCl₃): d6.77 (dd, 4H); δd4.45 (s, 1H); d3.89 (t, 2H); d1.75 (p,2H); d1.43 (p, 2H); d1.33-1.26 (m, 16H); d0.88 (t, 3H).

The synthesized 4-docecyloxyphenol (9.8 g, 35.2 mmol), methacrylic acid(6.0 g, 69.7 mmol), DCC (dicyclohexylcarbodiimide) (10.8 g, 52.3 mmol)and DMAP (p-dimethylaminopyridine) (1.7 g, 13.9 mmol) were placed in theflask and 120 mL of methylene chloride was added thereto, and thenreacted at room temperature for 24 hours under nitrogen. Aftercompletion of the reaction, the salt (urea salt) generated during thereaction was filtered off and the remaining methylene chloride was alsoremoved. Impurities were removed using hexane and DCM (dichloromethane)as the mobile phase in column chromatography and the product obtainedagain was recrystallized in a mixed solvent of methanol and water (1:1mix) to obtain the target product (7.7 g, 22.2 mmol) in a white solidphase in a yield of 63%.

<NMR Analysis Result>

¹H-NMR (CDCl₃): d7.02 (dd, 2H); δd6.89 (dd, 2H); d6.32 (dt, 1H); d5.73(dt, 1H); d3.94 (t, 2H); δd 2.05 (dd, 3H); d1.76 (p, 2H); δd1.43 (p,2H); 1.34-1.27 (m, 16H); d0.88 (t, 3H).

In Formula A, R is a linear alkyl group having 12 carbon atoms.

GIWAXS, XRD and DSC Analyses

A homopolymer was prepared using the monomer (A) of Preparation Example1, and GIWAXS and DSC were analyzed for the prepared homopolymer. Here,the homopolymer was prepared by a method of synthesizing a macromonomerusing the monomer (A) in the following examples. FIG. 2 shows theresults of GIWAXS analysis of the homopolymer. In FIG. 2, R square (Rsquare) was about 0.264 upon Gauss fitting. As a result of the DSCanalysis for the homopolymer, the corresponding polymer showed a meltingtemperature of about −3° C. and an isotropic transition temperature ofabout 15° C. Also, the ratio (M/I) of the area (M) of the meltingtransition peak to the area (I) of the isotropic transition peak in theDSC analysis of the homopolymer was about 3.67, the half-value width ofthe peak in an azimuthal angle of −90 degrees to −70 degrees of thediffraction pattern of the scattering vector in a range of 12 nm⁻¹ to 16nm⁻¹ in GIWAXS was about 48 degrees, and the half-value width of thepeak in an azimuthal angle of 70 degrees to 90 degrees of thediffraction pattern of the scattering vector in a range of 12 nm⁻¹ to 16nm⁻¹ in GIWAXS was about 58 degrees. Furthermore, in the X-raydiffraction analysis (XRD), a peak having a half-value width of about0.57 nm⁻¹ or so was observed at a scattering vector value of 1.96 nm⁻¹.

Preparation Example 2. Synthesis of Block Copolymer

2.0 g of the monomer (A) of Preparation Example 1, 64 mg ofcyanoisoproyl dithiobenzoate as an RAFT (reversibleaddition-fragmentation chain transfer) reagent, 23 mg of AIBN(azobisisobutyronitrile) as a radical initiator and 5.34 mL of benzenewere placed in a 10 mL Schlenk flask and stirred at room temperature for30 minutes under a nitrogen atmosphere, and then an RAFT (reversibleaddition-fragmentation chain transfer) polymerization reaction wasperformed at 70° C. for 4 hours. After the polymerization, the reactionsolution was precipitated in 250 mL of methanol as an extractionsolvent, and then filtered under reduced pressure and dried to prepare apink macro initiator. The yield of the macro initiator was about 82.6 wt% and the number average molecular weight (Mn) and molecular weightdistribution (Mw/Mn) were 9,000 and 1.16, respectively. 0.3 g of themacro initiator, 2.7174 g of a pentafluorostyrene monomer and 1.306 mLof benzene were placed in a 10 mL Schlenk flask and stirred at roomtemperature for 30 minutes under a nitrogen atmosphere, and then an RAFT(reversible addition-fragmentation chain transfer) polymerizationreaction was performed at 115° C. for 4 hours. After the polymerization,the reaction solution was precipitated in 250 mL of methanol as anextraction solvent, and then filtered under reduced pressure and driedto prepare a pale pink polymer segment copolymer. The yield of the blockcopolymer was about 18 wt %, and the number average molecular weight(Mn) and the molecular weight distribution (Mw/Mn) were 14,800 and 1.13,respectively. The block copolymer comprises a polymer segment A, whichis derived from the monomer (A) of Preparation Example 1 and has 12chain-forming atoms (the number of carbon atoms of R in Formula A), anda polymer segment B derived from the pentafluorostyrene monomer. Here,the volume fraction of the polymer segment A was about 0.45, and thevolume fraction of the polymer segment B was about 0.55. The surfaceenergy and density of the polymer segment A of the block copolymer were30.83 mN/m and 1 g/cm³, respectively, and the surface energy and densityof the polymer segment B were 24.4 mN/m and 1.57 g/cm³, respectively.Also, the result obtained by substituting the number of chain-formingatoms (12) in the polymer segment A of the block copolymer and thescattering vector value (q) in which the peak having the largest peakarea was identified in the scattering vector range of 0.5 nm⁻¹ to 10nm⁻¹ upon the X-ray diffraction analysis into the equation nq/(2×π),respectively, was about 3.75.

Preparation Example 3. Synthesis of Stripe Pattern Polymer (D1)

2.77 g of the monomer (A) of Preparation Example 1, 0.14 g of glycidylmethacrylate, 0.16 g of AIBN (azobisisobutyronitrile) and 7.5 mL oftetrahydrofuran (THF) were placed in a 10 mL flask, and a free radicalpolymerization reaction was performed at 60° C. for 12 hours under anitrogen atmosphere. After the polymerization, the reaction solution wasprecipitated in 250 mL of methanol as an extraction solvent, and thenfiltered under reduced pressure and dried to prepare a polymer. Thenumber average molecular weight (Mn) of the polymer (D1) for the stripepattern was determined to be 26,500 g/mol.

Preparation Example 4. Synthesis of Stripe Pattern Polymer (D2)

1.25 g of PFS (pentafluorostyrene), 0.14 g of glycidyl methacrylate,0.16 g of AIBN (azobisisobutyronitrile) and 2 mL of tetrahydrofuran(THF) were placed in a 10 mL flask, and a free radical polymerizationwas performed at 60° C. for 12 hours under a nitrogen atmosphere. Therelevant synthesis was performed in the same manner as in PreparationExample 3. The number average molecular weight (Mn) of the polymer (D2)for the stripe pattern was determined to be 59,400 g/mol.

Preparation Example 5. Synthesis of Stripe Pattern Polymer (D3)

1.25 g of the monomer (A) of Preparation Example 1, 0.14 g of glycidylmethacrylate, 0.16 g of AIBN (azobisisobutyronitrile) and 0.8 mL oftetrahydrofuran (THF) were placed in a 10 mL flask, and a free radicalpolymerization reaction was performed at 60° C. for 12 hours under anitrogen atmosphere. The relevant synthesis was performed in the samemanner as in Preparation Example 3. The number average molecular weight(Mn) of the polymer (D3) for the stripe pattern was determined to be99,500 g/mol.

Preparation Example 6. Synthesis of Stripe Pattern Polymer (D4)

1.25 g of PFS (pentafluorostyrene), 0.14 g of glycidyl methacrylate,0.16 g of AIBN (azobisisobutyronitrile) and 0.5 mL of tetrahydrofuran(THF) were placed in a 10 mL flask, and a free radical polymerizationreaction was performed at 60° C. for 12 hours under a nitrogenatmosphere. The relevant synthesis was performed in the same manner asin Preparation Example 3. The number average molecular weight (Mn) ofthe polymer (D4) for the stripe pattern was determined to be 110,500g/mol.

Preparation Example 7. Synthesis of Stripe Pattern Polymer (D5)

2.77 g of the monomer (A) of Preparation Example 1, 0.14 g of glycidylmethacrylate, 0.16 g of AIBN (azobisisobutyronitrile) and 20 mL oftetrahydrofuran (THF) were placed in a 50 mL flask, and a free radicalpolymerization reaction was performed at 60° C. for 12 hours under anitrogen atmosphere. The relevant synthesis was carried out in the samemanner as in Preparation Example 3. The number average molecular weight(Mn) of the polymer (D5) for the stripe pattern was determined to be17,200 g/mol.

Preparation Example 8. Synthesis of Stripe Pattern Polymer (D6)

2.77 g of the monomer (A) of Preparation Example 1, 0.14 g of glycidylmethacrylate, 0.16 g of AIBN (azobisisobutyronitrile) and 26 mL oftetrahydrofuran (THF) were placed in a 50 mL flask, and a free radicalpolymerization reaction was performed at 60° C. for 12 hours under anitrogen atmosphere. The relevant synthesis was performed in the samemanner as in Preparation Example 3. The number average molecular weight(Mn) of the polymer (D6) for the stripe pattern was determined to be10,200 g/mol.

Preparation Example 9. Synthesis of Stripe Pattern Polymer (D7)

2.77 g of PFS (pentafluorostyrene), 0.14 g of glycidyl methacrylate,0.16 g of AIBN (azobisisobutyronitrile) and 35 mL of tetrahydrofuran(THF) were placed in a 50 mL flask, and a free radical polymerizationreaction was performed at 60° C. for 12 hours under a nitrogenatmosphere. The relevant synthesis was performed in the same manner asD1 of Preparation Example 3. The number average molecular weight (Mn) ofthe polymer (D7) for the stripe pattern was determined to be 4,300g/mol.

Example 1

A polymer stripe pattern was formed on a silicon wafer substrate in thefollowing manner. First, the polymer (D6) of Preparation Example 8 wascoated to a thickness of about 10 nm on the substrate at the end andthermally annealed at 200° C. for 5 minutes to form a polymer film. Thecoating was performed by spin-coating a coating liquid prepared bydissolving the polymer (D6) in fluorobenzene to a concentration of about0.5 wt %. A resist film (hydridosilsesquioxane (HSQ), negative-toneresist layer) was formed on the polymer film to a thickness of about 100nm, and the resist film was patterned by an e-beam lithographic process.Subsequently, the polymer film was etched by an RIE (reactive ionetching) method using the patterned resist film as a mask, and theresidue was removed to form a polymer stripe pattern as shown in FIG. 1.The width (W) of the formed pattern was about 10 nm, and the pitch (F)was about 150 nm.

A polymer film was formed on the substrate having the pattern formed asabove using the block copolymer of Preparation Example 2. Specifically,a coating liquid prepared by diluting the block copolymer in toluene toa solid concentration of about 1.0 wt % was spin-coated on the patternof the substrate to a thickness of about 25 nm, dried at roomtemperature for about 1 hour, and thermally annealed at a temperature of160° C. for about 1 hour to form a self-assembled film. For the formedfilm, an SEM (scanning electron microscope) image was taken. FIG. 3 isan SEM image of the self-assembled film. The self-assembled film formeda vertically oriented lamellar phase, where the pitch was about 17 nm.It can be confirmed from FIG. 3 that a vertically oriented lamellarpattern with improved linearity by being highly aligned has beenappropriately formed.

Example 2

The process was performed in the same manner as in Example 1, except forusing the polymer (D5) of Preparation Example 7 upon forming the polymerstripe pattern. A polymer film was applied, which formed by coating acoating liquid prepared by dissolving the polymer in fluorobenzene to aconcentration of about 0.2 wt % on a substrate to a thickness of about10 nm and thermally annealing it at 200° C. for 5 minutes. As a resultof confirmation, as in Example 1, the self-assembled film formed avertically oriented lamellar phase and a highly aligned structure withimproved linearity was derived, where the pitch was about 17 nm.

Example 3

The process was performed in the same manner as in Example 1, except forusing the polymer (D1) of Preparation Example 3 upon forming the polymerstripe pattern. As a result of confirmation, as in Example 1, theself-assembled film formed a vertically oriented lamellar phase and ahighly aligned structure with improved linearity was derived, where thepitch was about 17 nm.

Example 4

The process was performed in the same manner as in Example 3, providedthat after the coating of the polymer D1, the polymer film was formed bythermally annealing it at 140° C. for 5 minutes. FIG. 4 shows theresults of the relevant process, and as in Example 1, the self-assembledfilm formed a vertically oriented lamellar phase and a highly alignedstructure with improved linearity was derived, where the pitch was about17 nm.

Example 5

The process was performed in the same manner as in Example 1, exceptthat the polymer (D2) of Preparation Example 4 was applied upon formingthe polymer stripe pattern, and the thermal annealing for forming thepolymer film proceeded at 120° C. for 5 minutes. As a result ofconfirmation, as in Example 1, the self-assembled film formed avertically oriented lamellar phase and a highly aligned structure withimproved linearity was derived, where the pitch was about 17 nm.

Example 6

The process was performed in the same manner as in Example 1, exceptthat the polymer (D3) of Preparation Example 5 was applied upon formingthe polymer stripe pattern, and the thermal annealing for forming thepolymer film proceeded at 100° C. for 5 minutes. FIG. 5 is the result ofExample 6, and as a result of confirmation, as in Example 1, theself-assembled film formed a vertically oriented lamellar phase and ahighly aligned structure with improved linearity was derived, where thepitch was about 17 nm.

Comparative Example 1

The process was performed in the same manner as in Example 1, exceptthat the polymer (D7) of Preparation Example 9 was applied upon formingthe polymer stripe pattern, and the thermal annealing for forming thepolymer film proceeded at about 300° C. for 5 minutes. FIG. 6 is theresult of Comparative Example 1, and in the case of Comparative Example1, as a result of confirmation, the highly aligned structure withlinearity as Examples was not derived, and the pattern also showed ashape that the horizontal orientation and the vertical orientation weremixed.

Comparative Example 2

The process was performed in the same manner as in Example 1, exceptthat the polymer (D4) of Preparation Example 6 was applied upon formingthe polymer stripe pattern, and the thermal annealing for forming thepolymer film proceeded at about 300° C. for 5 minutes. FIG. 7 is theresult of Comparative Example 2, and in the case of Comparative Example2, as a result of confirmation, the highly aligned structure withlinearity as Examples was not derived, and the pattern also showed ashape that the horizontal orientation and the vertical orientation weremixed.

1. A laminate comprising a substrate; a polymer stripe pattern formed ona surface of the substrate; and a block copolymer film formed on thesurface of the substrate on which the polymer stripe pattern is formed,wherein the block copolymer film comprises a block copolymer comprisinga polymer segment A satisfying one or more of Conditions 1 to 3 belowand a polymer segment B different from the polymer segment A and havingan absolute value of a difference in surface energy with the polymersegment A of 10 mN/m or less, and the polymer stripe pattern comprises apolymer, which satisfies one or more of Conditions 1 to 3 below, or hasan absolute value of a difference in surface energy with the polymersegment A of 10 mN/m or less and a number average molecular weight of 8Kg/mol to 100 Kg/mol: Condition 1: it exhibits a melting transition peakor an isotropic transition peak in a range of −80° C. to 200° C. in adifferential scanning calorimetry (DSC) analysis, Condition 2: itexhibits a peak having a half-value width in a range of 0.2 to 0.9 nm⁻¹within a scattering vector (q) range of 0.5 nm⁻¹ to 10 nm⁻¹ in an X-raydiffraction (XRD) analysis, Condition 3: it comprises a side chain,which satisfies Equation 1:3 nm⁻¹ to 5 nm⁻¹ =nq/(2×π)  [Equation 1] wherein, n is a number ofchain-forming atoms in the side chain and q is the smallest scatteringvector in which a peak is observed in the XRD analysis for the blockcopolymer or the scattering vector in which a peak of the largest peakarea is observed.
 2. The laminate according to claim 1, wherein theblock copolymer film is in direct contact with the substrate or thepolymer stripe pattern.
 3. The laminate according to claim 1, whereinthe block copolymer film forms a lamellar structure.
 4. The laminateaccording to claim 3, wherein the polymer stripe pattern has a stripewidth in a range of 0.3 L to 2.0 L, and the ratio (F/W) of the pitch (F)and the width (W) of the pattern is in a range of 2 to 20 and thepolymer stripe pattern has a thickness of 1 L or less, where L is apitch of the lamellar structure.
 5. The laminate according to claim 4,wherein the block copolymer film has a thickness in a range of 1 L to 10L, where L is a pitch of the lamellar structure.
 6. The laminateaccording to claim 4, wherein the polymer segment A in the blockcopolymer has a volume fraction in a range of 0.4 to 0.8, the polymersegment B has a volume fraction in a range of 0.2 to 0.6, and the sum ofthe volume fractions of the polymer segments A and B is
 1. 7. Thelaminate according to claim 1, wherein the polymer segment A comprises aside chain having 8 or more chain-forming atoms.
 8. The laminateaccording to claim 7, wherein the polymer segment A comprises a ringstructure and the side chain is substituted on the ring structuredirectly or via a linker.
 9. The laminate according to claim 8, whereinno halogen atom is present in the ring structure.
 10. The laminateaccording to claim 7, wherein the polymer segment B comprises three ormore halogen atoms.
 11. The laminate according to claim 10, wherein thepolymer segment B comprises a ring structure and the halogen atoms aresubstituted on the ring structure.
 12. A method for producing apatterned substrate comprising coating a coating liquid on a polymerstripe pattern of a substrate, wherein the coating liquid comprises ablock copolymer, which comprises a polymer segment A satisfying one ormore of Conditions 1 to 3 below and a polymer segment B different fromthe polymer segment A and having an absolute value of a difference insurface energy with the polymer segment A of 10 mN/m or less, andwherein the polymer stripe pattern is formed on a surface of thesubstrate, and forming a self-assembled structure of the blockcopolymer, wherein the polymer stripe pattern comprises a polymer, whichsatisfies one or more of Conditions 1 to 3 below, or has an absolutevalue of a difference in surface energy with the polymer segment A of 10mN/m or less and a number average molecular weight of 8 Kg/mol to 100Kg/mol: Condition 1: it exhibits a melting transition peak or anisotropic transition peak in a range of −80° C. to 200° C. in adifferential scanning calorimetry (DSC) analysis, Condition 2: itexhibits a peak having a half-value width in a range of 0.2 to 0.9 nm⁻¹within a scattering vector (q) range of 0.5 nm⁻¹ to 10 nm⁻¹ in an X-raydiffraction (XRD) analysis, Condition 3: it comprises a side chain,which satisfies Equation 1 below:3 nm⁻¹ to 5 nm⁻¹ =nq/(2×π)  [Equation 1] wherein, n is a number of thechain-forming atoms and q is the smallest scattering vector in which apeak is observed in the XRD analysis for the block copolymer or thescattering vector in which a peak of the largest peak area is observed.13. The method for producing a patterned substrate according to claim12, wherein the polymer stripe pattern is prepared by a methodcomprising steps of: (1) forming a polymer film on a substrate; (2)forming a resist film on the polymer film and patterning the resistfilm; and (3) etching the polymer film using the patterned resist filmas a mask.
 14. The method for producing a patterned substrate accordingto claim 12, further performing steps of selectively removing any onepolymer segment of the block copolymer on which the self-assembledstructure is formed; and etching the substrate using the blockcopolymer, from which the polymer segment is removed, as a mask.
 15. Thelaminate according to claim 1, wherein q is the scattering vector in arange of 0.5 nm⁻¹ to 10 nm⁻¹.
 16. The laminate according to claim 9,wherein the ring structure is an aromatic or an alicyclic ring.
 17. Thelaminate according to claim 7, wherein the chain-forming atoms are eachindependently a carbon, an oxygen, a sulfur or a nitrogen atom.
 18. Thelaminate according to claim 8, wherein the linker is an oxygen atom, asulfur atom, —NR₁—, —S(═O)₂—, a carbonyl group, an alkylene group, analkenylene group, an alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—, whereinR₁ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, analkoxy group or an aryl group, and X₁ is a single bond, an oxygen atom,a sulfur atom, —NR₂—, —S(═O)₂—, an alkylene group, an alkenylene groupor an alkynylene group, where R₂ is hydrogen, an alkyl group, an alkenylgroup, an alkynyl group, an alkoxy group or an aryl group.